Synthesis of New Poly(ether ketone)s Derived from Biobased Diols

Polymer, 2015

A route for the introduction of functional groups to poly(ether ether ketone) analogues, via a reactivity ratio controlled polycondensation process, has been developed. The reactivity differences, toward nucleophilic aromatic substitution reactions, of the three electrophilic sites in 3,4',5-trifluorobenzophenone, 1, affords the opportunity to prepare functionalized B 2-type monomers in situ, followed by polycondensation with the appropriate bisphenol to prepare the corresponding linear polymer. The reactivity differences in 1 were probed via a combination of 13 C and 19 F NMR spectroscopy along with model reactions using m-cresol as the nucleophile. Reaction of 1 with 1.03 molar equivalents of a series of phenols provided the desired B 2-type monomers in high selectivity. The B 2-type monomers were then converted to the linear polymers by reaction with Bisphenol-A and their structures were confirmed via NMR spectroscopy. The thermal properties were evaluated by a combination of thermogravimetric analysis and differential scanning calorimetry.

Journal of Polymer Science Part A: Polymer Chemistry, 1994

Aromatic poly (ether-ketone-amide) s were prepared by the palladium-catalyzed polycondensation of aromatic dibromides containing ether ketone units, aromatic diamines, and carbon monoxide. Polymerizations were carried out in N,N-dimethylacetamide (DMAc) in the presence of palladium catalyst, triphenylphosphine, and 1,8-diazabicyclo [ 5,4,0]-7undecene (DBU) , and resulted in poly (ether-ketone-amide) s with inherent viscosities up to 0.82 dL/g under mild conditions. The polymers were quite soluble in strong acid, dipolar aprotic solvents, and pyridine. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 400°C in nitrogen atmosphere. The glass transition temperatures of the polymers were about 200°C, which are higher than those of poly(ether-ketone) analogues. These polymers also showed good tensile strength and tensile modulus.

Journal of Polymer Science Part A: Polymer Chemistry, 1998

Linear polyaryl(ether ketones) containing tert-butyl pendent groups were prepared from aromatic hydrocarbons and aromatic diacid chlorides, both classes of monomers containing tert-butyl pendent groups. The polymers were prepared in high yield and high molecular weight by low-temperature precipitation polycondensation in 1,2-dichloroethane. The presence of meta-oriented moieties and bulky pendent groups played a beneficial role with regard to solubility, while the thermal transitions and thermal resistance were not greatly impaired relative to conventional all para-oriented polyaryl(ether-ketones). The current polyaryl(ether-ketones) showed glass transition temperatures in the range 170-240ЊC and decomposition temperatures, as measured by TGA, of about 500ЊC.

Macromolecular Chemistry and Physics, 2005

Polymer, 1996

The synthesis of a soluble poly(ether ketone) (PEK) precursor via a ketimine route is described. The synthesis is realized by using a halogenophenol monomer, i.e. N-(4-fluoro-4'-hydroxydiphenylmethylene) imine. First we describe the synthesis of the monomer and its characterization by infra-red and 13C nuclear magnetic resonance spectroscopies. Subsequently, the polymerization of the monomer is reported and the factors influencing the polymerization reaction are considered. The ketimine PEK prepolymer is soluble in common organic solvents. The rate of the ketimine PEK condensation is decreased compared with that of the equivalent ketimine poly(ether ether ketone) condensation due to the deactivation of the reactive intermediate (Meisenheimer's complex). The poly(ether ketimine) can be readily hydrolysed to the poly(ether ketone).

International Journal of Molecular Sciences, 2014

Poly(alkylene dicarboxylate)s constitute a family of biodegradable polymers with increasing interest for both commodity and speciality applications. Most of these polymers can be prepared from biobased diols and dicarboxylic acids such as 1,4-butanediol, succinic acid and carbohydrates. This review provides a current status report concerning synthesis, biodegradation and applications of a series of polymers that cover a wide range of properties, namely, materials from elastomeric to rigid characteristics that are suitable for applications such as hydrogels, soft tissue engineering, drug delivery systems and liquid crystals. Finally, the incorporation of aromatic units and α-amino acids is considered since stiffness of molecular chains and intermolecular interactions can be drastically changed. In fact, poly(ester amide)s derived from naturally occurring amino acids offer great possibilities as biodegradable materials for biomedical applications which are also extensively discussed.

Journal of Polymer Science Part A: Polymer Chemistry, 1995

Attempts were made to synthesize poly(ether-su1fone)s from aliphatic diols or bissilylated diols on the one hand, and 4,4'-dichlorodiphenylsulfone or 4,4'-difluorodiphenylsulfone on the other hand. The reaction conditions and the catalyst were varied. Polycondensations of silylated diols with 4,4'-difluorodiphenylsulfone and powdered K&03 in N-methylpyrrolidone proved to give the best results. Using silylated isosorbide and isomannide as monomers chiral poly(ether-su1fone)s were prepared. GPC measurements indicate weight-average molecular weights in the range of 27 X 103-200 X lo3. 0 1995 John W i l e y & Sons, Inc.

Journal of Molecular Catalysis B: Enzymatic, 2012

Natural R-(−)-xanthorrhizol possess a number of therapeutic activities including anti-cancer. The pharmacokinetic properties of that poorly aqueous soluble compound could be improved by incorporating it into polymeric materials. Glycerol can produce a functionalized polymer through a polycondensation process. Enzymatic polycondensation of glycerol and divinylesters was studied and xanthorrhizol was covalently loaded via a butanedioate linker to the polymer backbone. It was observed that xanthorrhizol loading to the polymer backbone increases with the increasing of the chain length of a dioate moiety. Enzyme-mediated xanthorrhizol release from a polymer backbone shows that the polymeric prodrug is able to release xanthorrhizol in a sustained manner. Therefore, the approach described here might be valuable for controlled loading and release of such phenolic sesquiterpenes from the polymeric prodrug.

Macromolecular Chemistry and Physics, 1996

Bis(b-naphthoxy)benzonitrile (BNOBN) was synthesized by reaction of b-naphthol with 2,6-difluorobenzonitrile in N-methyl-2-pyrrolidone (NMP) in the presence of KOH and K 2 CO 3. Poly(ether ketone ether ketone ketone)(PEKEKK) /poly(ether ether ketone ketone) (PEEKK) copolymers containing naphthalene and pendant cyano groups were obtained by electrophilic Friedel-Crafts polycondensation of terephthaloyl chloride (TPC) with varying mole proportions of 4,4 0-diphenoxybenzophenone (DPOBP) and 2,6-bis(b-naphthoxy)benzonitrile (BNOBN) using 1,2dichloroethane (DCE) as solvent and NMP as Lewis base in the presence of anhydrous AlCl 3. The resulting polymers were characterized by various analytical techniques, such as FTIR, DSC, TG, and WAXD. The results indicated that the crystallinity and melting temperature of the polymers decreased with increase in concentration of the BNOBN units in the polymer, the glass transition temperature of the polymers increased with increase in concentration of the BNOBN units in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 536 C in N 2 atmosphere. The copolymers have good resistance to acidity, alkali, and organic solvents. Because of the melting temperature (T m) depression with increase in the BNOBN content in the reaction system, the processability of the resultant coplymers could be effectively improved. V

Journal of Polymer Science Part A: Polymer Chemistry, 1989

The known polymerization of 4,4'-difluorobenzophenone (DFB) with the &anion of hydroquinone to poly(pheny1ene ether ether ketone) (PEEK) and polymerization of either DFB with the dianion of 4,4'-dihydroxybenzophenone or self polycondensation of the anion of 4-hydroxy-4'-fluoro-benzophenone to poly(pheny1ene ether ketone) (PEK) were studied in N-cyclohexyl-2pyrrolidone (CHP), which is a high-boihg aprotic polar solvent. The formation of high-molecular weight PEEK and PEK in this solvent was very efficient. The reactivity in CHP can be ascribed to effective solvation of metal ions rendering the anion very reactive toward nucleophilic substitution. The polymerization was extended to 4,4'-bis(4-fluorobenzoyl)diphenyl ether and 1,4-bi~4-(4-fluorobenzoyl)phenoxy]benzene to give a high molecular weight polymer with PEK and PEEK repeating units and PEEK respectively. The polymerization of DFB with purified anhydrous sodium sulfide in CHP gave rapidly a high molecular weight poly(pheny1ene ketone sulfide) (PKS). In contrast, diphenyl sulfone (DPS) was not very effective in obtaining such a high molecular weight PKS even with prolonged heating, which suggests the uniqueness of CHP in promoting a high degree of polymerization.